Process for the preparation of phosphoric monoester

ABSTRACT

An organic hydroxyl compound is reacted with a phosphorylating agent comprising phosphorus pentaoxide and at least one compound selected from the group consisting of water, phosphoric acid and polyphosphoric acid and having a value represented by formula (I) of from 0.5 to 1.0, under such a condition that the ratio as defined by formula (II) has a value in the range of from 2.8 to 3.2; or alternatively, an organic hydroxyl compound is reacted with the above phosphorylating agent under such a condition that the ratio as defined by formula (II) has a value in the range of from exceeding 3.2 up to 6.4 and then phosphorus pentaoxide is added to the reaction product in such an amount that the ratio as defined by formula (II) has a value in the range of from 2.8 to 3.2 with respect to the total feeds of the starting materials to conduct further reaction: ##EQU1## The above process produces a phosphoric ester mixture that is excellent in hue and odor, is reduced in the amount of orthophosphoric acid and contains a phosphoric monoester useful as a component of a detergent.

This application is a continuation of Ser. No. 08/849,211, filed Jun. 9,1997, which is the National Stage of PCT International Application No.PCT/JP95/01891, filed Sep. 20, 1995.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for the preparation of aphosphoric monoester through the phosphorylating of an organic hydroxylcompound. More particularly, the present invention relates to a processfor the preparation of a phosphoric monoester which can easily provide aphosphoric ester mixture having a high phosphoric monoester purity, areduced orthophosphoric acid content, and good odor and hue.

2. Description of the Related Art

Phosphoric esters of organic hydroxyl compounds are used in a wide fieldas a detergent, a textile treating agent, an emulsifying agent, a rustpreventive, a liquid ion exchanger and a medicament.

Although the reaction of an organic hydroxyl compound with phosphoruspentoxide has been known as an industrial process for the preparation ofa phosphoric ester in the prior art, the product of the reactioncomprises mainly a nearly equimolar mixture of a phosphoric monoesterrepresented by the following formula (A) and a phosphoric diesterrepresented by the following general formula (B) (hereinafter, thismixture is referred to as "sesquiphosphate"): ##STR1## wherein Rrepresents a residue which is obtained by eliminating one hydroxyl groupfrom an organic hydroxyl compound.

There are great differences in properties between a phosphoric monoesterand a phosphoric diester. For example, alkali metal salts andalkanolamine salts of phosphoric monoester of long-chain alkyl alcohols(e.g., lauryl alcohol) are soluble in water, excellent in foaming powerand detergency, less toxic and lowly irritant to the skin to be usefulas an excellent detergent, while alkali metal salts and alkanolaminesalts of phosphoric diesters of long-chain alkyl alcohols are littlesoluble in water and exhibit foam inhibiting properties rather thanlittle exhibit a foaming power. Therefore, a sesquiphosphate saltcontaining a large amount of a phosphoric diester salt are unusable as ahighly foaming detergent.

Under these circumstances, the development of a process by which aphosphoric ester mixture having a high phosphoric monoester content canbe prepared on an industrial scale safely and easily has been eagerlyexpected and the following processes have been reported to answer thisexpectation:

(1) a process which comprises reacting an organic hydroxyl compound withphosphorus oxychloride and hydrolyzing the obtained monoalkylphosphorodichloridate;

(2) a process which comprises adding water to an organic hydroxylcompound and thereafter adding phosphorus pentoxide to the obtainedmixture to conduct phosphorylating with the amount of water preliminaryadded being 0.5 to 3 mol per mol of phosphorus pentoxide;

(3) a process which comprises reacting an organic hydroxyl compound withorthophosphoric acid and phosphorus pentoxide (Japanese PatentPublication-B 42-6730, published on Mar. 18, 1967);

(4) a process which comprises reacting an organic hydroxyl compound witha condensed phosphoric acid (polyphosphoric acid);

(5) a process which comprises reacting an organic hydroxyl compound witha condensed phosphoric acid (polyphosphoric acid) and then recovering,concentrating and reusing excess phosphoric acid;

(6) a process which comprises reacting an organic hydroxyl compound witha phosphorylating agent comprising phosphorus pentoxide, phosphoric acidand a polyphosphoric acid under such a condition that phosphoric acidcomponents are excess, adding an organic hydroxyl compound to theobtained reaction mixture to make up to a stoichiometric amount andconducting further phosphorylating [see U.S. Pat. No. 4,350,645(published on Sep. 21, 1982, assignee: Kao Corporation)]; and

(7) a process which comprises reacting an organic hydroxyl compound withphosphorus pentoxide in the presence of water while blowing steam intothe reaction system.

However, these processes have respective disadvantages as will now bedescribed, being unsatisfactory as industrial processes for thepreparation of phosphoric monoester.

According to the process (1), three mol of hydrogen chloride isgenerated in order to prepare one mol of a phosphoric monoester.Accordingly, the process (1) is problematic in the disposal of hydrogenchloride and working atmosphere. Further, according to the process (1),an alkyl chloride is formed as a by-product owing to the presence ofhydrogen chloride, so that it is difficult to enhance the phosphoricmonoester content of the reaction product.

According to the processes (2) and (3), an organic hydroxyl compoundcomes into direct contact with highly active phosphorus pentoxide fromthe first, though a small amount of water or orthophosphoric acid ispresent in the reaction system. Therefore, a sesquiphosphate containinga phosphoric diester is formed to lower the purity of the reactionproduct for a phosphoric monoester. Additionally, these processes have adisadvantage in that the phosphoric monoester formed is decomposed tocause the discoloration of the reaction product and the generation of anasty odor. When an increased amount of water or orthophosphoric acid isused in order to lower the activity of phosphorus pentoxide, theorthophosphoric acid content of the product is increased. Thecontamination of the product with orthophosphoric acid has undesirableinfluences on some fields, so that the use of the product is limited.For example, when monosodium salt of a phosphoric monoester of along-chain alkyl alcohol is employed for a paste detergent, disodiumphosphate is deposited due to the present of a large amount oforthophosphoric acid. The deposition of disodium phosphate isunfavorable in the use of the detergent.

According to the process (4), a phosphoric mono-ester can be selectivelyprepared. However, the amount of orthophosphoric acid formed as aby-product is nearly equal to the reciprocal of the average degree ofcondensation of the polyphosphoric acid used, so that the contaminationof the product with orthophosphoric acid is unavoidable. Accordingly,the process (4) has the same problem as that of the processes (2) and(3). Further, the use of a polyphosphoric acid having an extremely highdegree of condensation is necessitated in order to decrease the amountof orthophosphoric acid formed as a by-product according to the process(4). However, in the industrial preparation of such a polyphosphoricacid, the reaction system becomes highly viscous and the materials ofthe reactor are limited, so that the industrial preparation thereof isextremely difficult.

According to the process (5), a phosphoric monoester can be selectivelyprepared. Further, the process involves the recovery and revitalizationof excess phosphoric acid, being industrially advantageous also in thisrespect. However, the process uses a large amount of phosphoric acid, sothat the recovery thereof necessitates the shouldering of various heavyburdens and the use of considerably complicated equipment. Accordingly,the process cannot easily be conducted.

According to the process (6), the organic hydroxyl compound is added intwo portions, so that the obtained reaction product has an enhancedratio of a phosphoric monoester to a phosphoric diester. However, thereaction system tends to become highly viscous under the condition of anexcess of the phosphorylating agent i.e., in the early stages of thereaction to necessitate the use of an industrially special reactor.According to the process (6), additionally, the decomposition of thephosphoric monoester formed proceeds, which lowers the yield of thephosphoric monoester and enhances the orthophosphoric acid content ofthe reaction product. The increase in the orthophosphoric acid contentof the reaction product has undesirable influences on some fields, sothat the use of the reaction product is limited.

According to the process (7), the ratio of the phosphoric monoester tothe phosphoric diester can be enhanced by blowing steam into thereaction system. However, the blowing of steam into the reaction systemincreases the amount of orthophosphoric acid formed. Accordingly, theprocess (7) has the same problem as that of the processes (2), (3) and(4).

As described above, the process using phosphorus oxychloride as aphosphorylating agent is problematic in that hydrogen chloride isgenerated, while that using a polyphosphoric acid is problematic in thatorthophosphoric acid is formed as a by-product and that the materials ofthe reactor are limited. Among the processes using phosphorus pentoxide,those involving the direct reaction of an organic hydroxyl compound withphosphorus pentoxide give a sesquiphosphate containing a phosphoricdiester, while that of reacting an organic hydroxyl compound with anexcess of a phosphorylating agent in order to lower the phosphoricdiester content of the reaction product is problematic in that thereaction system becomes viscous to result in difficult stirring and thata large amount of orthophosphoric acid is formed as a by-product.

The industrial processes for the preparation of phosphoric monoesteraccording to the prior art have been described above, among which thoseusing phosphorus pentoxide are advantageous in respect of equipment.Therefore, further improvement in the processes using phosphoruspentoxide has been expected eagerly.

DISCLOSURE OF THE INVENTION

Summary of the Invention

An object of the present invention is to provide an industrial processfor the preparation of a phosphoric monoester according to thephosphorus pentoxide method which gives a reduced amount oforthophosphoric acid formed as a by-product, can give a phosphoricmonoester selectively and in an enhanced yield, and is characterized inthat the obtained reaction product is excellent in hue and odor.

Another object of the present invention is to provide an industrialprocess for the preparation of a phosphoric monoester according to thephosphorus pentoxide method, by which the phosphorylating can be alwaysconducted in a low-viscosity system.

Under the circumstances described above, the present inventors have madeextensive studies on the industrial preparation of a phosphoricmonoester. As a result of the studies, they have found that a phosphoricester mixture which has good hue and odor and an enhanced monoestercontent and is reduced in the amount of phosphoric acid formed as aby-product can be prepared industrially efficiently by preliminarymixing the whole or part of the phosphorus pentoxide to be used in thereaction with at least one compound selected from the group consistingof water, phosphoric acid and a polyphosphoric acid to prepare aphosphorylating agent and adding an organic hydroxyl compound to thephosphorylating agent unlike the feeding order of starting materialsaccording to the prior art. The phosphorylating agent described abovetakes the form of a heterogeneous system wherein part of the phosphoruspentoxide fed remains undissolved. The present inventors have also foundthat an objective phosphoric monoester can be prepared without anyincrease in the viscosity of the reaction system specially by reactingan organic hydroxyl compound preliminary with the phosphorylating agentof which the amount is less than the stoichiometric one (i.e., with aphosphorylating agent prepared by using part of the phosphorus pentoxideto be used in the reaction), and adding the balance of phosphoruspentoxide to the obtained reaction product to make up to a total amountof ca. stoichiometric one. The present invention has been accomplishedon the basis of these findings.

Thus, the present invention provides a process for the preparation of aphosphoric monoester by reacting an organic hydroxyl compound with aphosphorylating agent comprising phosphorus pentoxide and at least onecompound selected from the group consisting of water, phosphoric acidand polyphosphoric acid, under such conditions that a) the ratio asdefined by formula (I) has a value in the range of from 0.5 to 1.0, andb) the ratio as defined by formula (II) has a value in the range of from2.8 to 3.2: ##EQU2##

The term "molar amount of organic hydroxyl compound" means theequivalent of hydroxyl group(s) derived from the organic hydroxylcompound.

According to this process, the synthesis of phosphoric esters(phosphorylating) having a high phosphoric monoester purity can begenerally achieved substantially only by the above one step.

Further, the present invention provides a process for the preparation ofa phosphoric monoester comprising:

(1) a first step of reacting an organic hydroxyl compound with aphosphorylating agent comprising phosphorus pentoxide and at least onecompound selected from the group consisting of water, phosphoric acidand polyphosphoric acid, under such conditions that a) the ratio asdefined by formula (I) has a value in the range of from 0.5 to 1.0 andb) the ratio as defined by formula (II) has a value in the range of fromexceeding 3.2 up to 6.4, and

(2) a second step, wherein phosphorus pentoxide is added in such anamount that the ratio represented by formula (II) has a value in therange of from 2.8 to 3.2.

According to this process, the synthesis of phosphoric esters(phosphorylating) having a high phosphoric monoester purity can begenerally achieved substantially only by the above two steps.

In the formulae (I) and (II), the phosphorylating mixture comprisingphosphorus pentoxide and polyphosphoric acid and/or phosphoric acid(i.e., orthophosphoric acid) and/or water is formally treated as P₂O₅.n(H₂ O) and called as "phosphorylating agent". The molar amount ofphosphorylating agent as defined in the formulae (I) and (II) representsthe amount (mol) of P₂ O₅ unit(s) derived from the phosphorylatingagent, which is introduced into the reaction system as the startingmaterial. The molar amount of water as defined in the formulae (I) and(II) represents the amount (mol) of water (H₂ O) derived from thephosphorylating agent, which is introduced into the reaction system asthe starting material. The water includes the bound water in thepolyphosphoric acid (P₂ O₅.xH₂ O) and/or orthophosphoric acid (1/2(P₂O₅.3H₂ O)), and free water.

In other words, the present invention relates to a process for thepreparation of a phosphoric ester characterized by reacting aphosphorylating agent prepared by mixing phosphorus pentoxide withwater, phosphoric acid or polyphosphoric acid or a mixture of them insuch a way that the value represented by the following formula (i):##EQU3## will be from 0.5 to 1.0 with an organic hydroxyl compound undersuch a condition that the value represented by the following formula(ii): ##EQU4## will be from 2.8 to 6.4, and, if necessary, furtheradding phosphorus pentoxide thereto in such a way that the valuerepresented by the following formula (iii): ##EQU5## will be from 2.8 to3.2 with respect to the total feeds to conduct a reaction.

The phosphorylating agent preferably comprises phosphorus pentoxide andat least one compound selected from the group consisting of water andphosphoric acid.

The phosphorylating agent may be one prepared by mixing phosphoruspentoxide with at least one compound selected from the group consistingof water, phosphoric acid and polyphosphoric acid either at 100° C. forup to 4 hours or at 50° C. for up to 10 hours. The phosphorylating agentthus prepared is heterogeneous owing to the presence of phosphoruspentoxide or its hydrate.

The reaction product obtained by the above process is preferablysubjected to hydrolysis and/or deodorization.

The organic hydroxyl compound is desirably a linear or branched,saturated or unsaturated alcohol having 6 to 30 carbon atoms, an adductof a linear or branched, saturated or unsaturated alcohol having 6 to 30carbon atoms with 1 or more alkylene oxide(s), wherein the alkyleneoxide has 2 to 4 carbon atoms and the number of alkylene oxide moleculesadded is 1 to 100, or an adduct of an alkylphenol, wherein the alkylmoiety has 6 to 20 carbon atoms, with 1 or more alkylene oxide(s),wherein the alkylene oxide has 2 to 4 carbon atoms and the number ofalkylene oxide molecules added is 1 to 100.

Furthermore, the present invention provides a phosphoric monoesterobtainable by the process according to the present invention.

The present invention will now be described in detail.

DETAILED DESCRIPTION OF THE INVENTION

The phosphorus pentoxide in the present invention is a compound alsocalled "phosphoric acid anhydride" and its molecular formula is P₄ O₁₀or P₂ O₅.

The phosphoric acid in the present invention refers to orthophosphoricacid represented by the following formula (C): ##STR2##

The phosphoric acid is generally available in the market as an aqueoussolution of phosphoric acid having a concentration of less than 100% byweight in terms of orthophosphoric acid equivalent (i.e., calculated asH₃ PO₄). The concentration is not particularly limited, but ispreferably 70 to 90% by weight.

The polyphosphoric acid is a condensate of orthophosphoric acidrepresented by the above formula (C), and has a pyrophosphate bond(s)(P--O--P) in the molecule. The polyphosphoric acid is generally onemember selected from the group consisting of linear condensed phosphoricacids represented by formula (F) which will be described below, branchedcondensed phosphoric acids, cyclic condensed phosphoric acids and cycliccondensed phosphoric acids having a side chain, or a mixture of two ormore of them. The polyphosphoric acid may also contain, as one componentthereof, orthophosphoric acid represented by the above formula (C).Examples of the linear condensed phosphoric acids include pyrophosphoricacid represented by formula (D) which will be described below andtripolyphosphoric acid represented by formula (E) which will bedescribed below. Examples of the branched condensed phosphoric acids,cyclic condensed phosphoric acids and cyclic condensed phosphoric acidshaving a side chain include compounds represented by the followingformulae (G), (H) and (I) respectively: ##STR3##

Polyphosphoric acid is a phosphoric acid having a concentration of 100%by weight or above in terms of orthophosphoric acid equivalent (i.e.,calculated as H₃ PO₄) and has a homogeneous transparent appearance. Thephosphoric acid concentration of the polyphosphoric acid to be used inthe present invention is preferably 100 to 120% by weight, though it isnot particularly limited.

The organic hydroxyl compound to be used in the present invention ispreferably an organic mono hydroxyl compound represented by the formula:ROH, though it is not limited thereto as long as it is an organichydroxyl compound having a hydroxyl group(s). Examples thereof includelinear or branched, saturated or unsaturated alcohols having 6 to 30,preferably 8 to 24 carbon atoms, adducts of the alcohols with analkylene oxide(s) (wherein the alkylene oxide has 2 to 4 carbon atomsand the number of alkylene oxide molecules added is 1 to 100), andadducts of alkylphenols (wherein the alkyl moiety has 6 to 20 carbonatoms) with an alkylene oxide(s) (wherein the alkylene oxide has 2 to 4carbon atoms and the number of alkylene oxide molecules added is 1 to100).

Specific examples of the organic hydroxyl compound include octanol,nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristylalcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol,2-ethylhexanol, isooctanol, isononanol, isodecanol, isotridecanol andsynthetic alcohols such as Oxo alcohol (a product of Nissan ChemicalIndustry Co. Ltd.), Diadol (a product of Mitsubishi Chemical Co. Ltd.),Dobanol (a product of Mitsubishi Petrochemical Co. Ltd.), Linevol (aproduct of Showa Shell Chemical Co. Ltd.), Neodol (a product of Shell)and Lial (a product of Eni Chem).

In the present invention, one of these organic hydroxyl compounds or amixture of two or more of them may be used.

According to the present invention, first, a phosphorylating agent isprepared by mixing phosphorus pentoxide with at least one compoundselected from the group consisting of water, phosphoric acid andpolyphosphoric acid in such a way that the ratio as defined by the aboveformula (I) has a value in the range of from 0.5 to 1.0, preferably from0.55 to 0.9, still more preferably from 0.60 to 0.85. It is preferableto mix phosphorus pentoxide with water and/or phosphoric acid,particularly preferably with an aqueous solution of phosphoric acid.

The phosphorylating agent thus prepared contains 0.5 to 1.0 mol of P₂ O₅unit per mol of water included in the phosphorylating agent representedas P₂ O₅.n(H₂ O). When the value is less than 0.5, the reaction of anorganic hydroxyl compound with the resulting phosphorylating agent willgive an increased amount of orthophosphoric acid owing to the high watercontent of the phosphorylating agent. On the contrary, when the valueexceeds 1.0, the resulting. phosphorylating agent contains highly activephosphorus pentoxide as such, so that the reaction of an organichydroxyl compound with the phosphorylating agent will be liable to givesesquiphosphate; and the phosphorylating agent will be viscous to makethe operations in the preparations of the phosphorylating agent and thephosphoric monoester difficult.

The order of feeding the starting materials in the preparation of thephosphorylating agent is not particularly limited as far as the finalcomposition satisfies the requirement with respect to the ratio asdefined by formula (I). However, it is preferable to add phosphoruspentoxide gradually to the other material(s) (water, phosphoric acidand/or polyphosphoric acid), because phosphorus pentoxide generates heatwhen mixed with water.

The phosphorylating agent according to the present invention may beheterogeneous. In other words, in the present invention, phosphoruspentoxide may be merely mixed with one compound selected from the groupconsisting of water, phosphoric acid and polyphosphoric acid. That is,it is not necessitated that they are reacted each other to give acompletely homogeneous polyphosphoric acid. In order to prepare acompletely homogeneous polyphosphoric acid, the starting materialmixture for the phosphorylating agent must be stirred at hightemperature or must be aged, and, therefore, another vessel forpreparing the phosphorylating agent is necessitated in addition to thereaction vessel in some case.

The phosphorylating agent prepared by mixing phosphorus pentoxide withat least one compound selected from the group consisting of water,phosphoric acid and polyphosphoric acid can be used as such, i.e., in aheterogeneous state, in the phosphorylating of an organic hydroxylcompound. It is unnecessary to age the phosphorylating agent by heatingprior to the use in the phosphorylating. However, the phosphorylatingagent may be stirred under heating to suit the convenience of thereaction. The phosphorylating agent cannot be generally converted into awholly homogeneous polyphosphoric acid even by stirring either at 90° C.for about 5 hours or at 50° C. for about 10 hours. The insoluble matterin this case is believed to be phosphorus pentoxide hydrate.

In order to attain the effect of the present invention more effectively,it is desirable that the amount of phosphorus pentoxide to be used inthis step is at least 30 mole %, more desirably at least 60 mole %, mostdesirably at least 70 mole % based on the whole amount of thephosphorylating agent calculated as P₂ O₅ unit(s).

According to a first embodiment of the present invention, thephosphorylating agent prepared above is reacted with an organic hydroxylcompound under such a condition that the value represented by the aboveformula (II) ranges from 2.8 to 3.2, which means that phosphorylatingagent (calculated as P₂ O₅ unit(s)) is initially fed in an amount of atleast about 0.91 mol per 2 equivalents of hydroxyl groups derived fromthe organic hydroxyl compound (i.e., in an amount of at least about 91%of the required theoretical amount). When the value represented by theabove formula (II) is less than 2.8, which means the presence of anexcess of phosphorylating agent, excess phosphorylating agent will befinally converted into orthophosphoric acid, so that the resultingreaction product will contain an increased amount of orthophosphoricacid unfavorably. Further, when the reaction is conducted under such acondition that the ratio as defined by the above formula (II) is lessthan 2.8, sesquiphosphate is formed with the formation oforthophosphoric acid as a by-product to fail in enhancing the monoestercontent of the reaction product.

The insolubles contained in the phosphorylating agent according to thepresent invention may dissolve in the reaction system with the advanceof the reaction between the organic hydroxyl compound with thephosphorylating agent.

The phosphorylating under such a condition that the ratio as defined bythe above formula (II) ranges from 2.8 to 3.2 is conducted understirring at generally 30 to 100° C., preferably 50 to 90° C. forgenerally 0.1 to 10 hours, preferably 0.1 to 8 hours. When the reactionis conducted under the conditions described above, the reaction will befully attained without the deterioration of the organic hydroxylcompound.

In the present invention, when an organic hydroxyl compound is reactedwith the phosphorylating agent under such a condition that the ratio asdefined by the above formula (II) ranges from 2.8 to 3.2, thephosphorylating can be generally attained substantially only by thisstep. In this case, however, the viscosity of the reaction systemsometimes increases during the reaction to necessitate the use of areactor such as kneader suitable for a highly viscous fluid. Therefore,the second embodiment of the present invention which will be describedbelow in detail is more preferable than the first embodiment of thepresent invention.

According to a second embodiment of the present invention, thephosphorylating agent is reacted with an organic hydroxyl compound in afirst step under such a condition that the ratio as defined by the aboveformula (II) ranges from higher than 3.2 to 6.4, which means thatphosphorylating agent (calculated as P₂ O₅ unit(s)) is initially fed inan amount of at least 0.37 mol per 2 equivalents of hydroxyl groupsderived from the organic hydroxyl compound (i.e., in an amount of atleast 37% of the required theoretical amount). When the first step ofthe reaction is conducted under such a condition that the ratio asdefined by the above formula (II) exceeds 6.4, a large amount ofunreacted alcohol remains in the reaction system. In this case, thereaction can be advanced by adding phosphorus pentoxide to the resultingreaction system after the completion of the reaction of the first step.However, a large amount of phosphorus pentoxide must be added to thereaction system to advance the reaction, which causes increase in theamount of sesquiphosphate formed to lower the purity of the reactionproduct for the phosphoric monoester unfavorably. The first step isconducted under such a condition that the ratio as defined by the aboveformula (II) has a value in the range of preferably from 3.5 to 5.5,still more preferably from 4.0 to 5.0.

The insolubles contained in the phosphorylating agent according to thepresent invention may dissolve in the reaction system with the advanceof the reaction between the organic hydroxyl compound with thephosphorylating agent.

The phosphorylating of the first step is conducted under stirring atgenerally 30 to 100° C., preferably 50 to 90° C. for generally 0.1 to 10hours, preferably 0.1 to 8 hours. When the reaction is conducted undersuch conditions, the reaction will be fully attained without thedeterioration of the organic hydroxyl compound.

According to the second embodiment of the present invention, after thecompletion of the reaction of the first step, phosphorus pentoxide insuch an amount that the ratio as defined by the above formula (II)ranges from 2.8 to 3.2 with respect to the total feeds of the startingmaterials is added to the reaction system to conduct furtherphosphorylating. That is, when the phosphorylating of an organichydroxyl compound is conducted under such a condition that the ratio asdefined by the above formula (II) ranges from 2.8 to 3.2 (i.e., thefirst embodiment of the present invention), additional phosphoruspentoxide need not be added for further phosphorylating, while when thephosphorylating is conducted under such a condition that the ratio asdefined by the above formula (II) exceeds 3.2 but is up to 6.4 (i.e.,the first step of the second embodiment of the present invention),phosphorus pentoxide in such an amount that the ratio as defined by theabove formula (II) will be in the range of from 2.8 to 3.2 isadditionally added to the reaction system to conduct furtherphosphorylating (the second step of the second embodiment of the presentinvention).

When the reaction of the second step is conducted under such a conditionthat the ratio as defined by the above formula (II) exceeds 3.2, thereaction will not be completed to make unreacted organic hydroxylcompound remain in the reaction system, while when it is conducted undersuch a condition that the ratio is less than 2.8, excess phosphorylatingagent will remain in the reaction system finally as orthophosphoricacid. Both of the cases are unfavorable.

The phosphorus pentoxide for the reaction of the second step may beadded by any of batchwise and semibatchwise methods. The latter ispreferable to prevent local reaction. The semibatchwise addition may beconducted by a stepwise or continuous method or a combination of both ofthem.

There may occurs an idea that POCl₃, poly-phosphoric acid or a mixtureof phosphorus pentoxide with water is added as the phosphorylating agentfor the second stage of the reaction. However, the addition of POCl₃ hasa disadvantage of generating hydrogen chloride as a by-product, whilethe use of the other phosphorylating agents has a disadvantage ofgenerating orthophosphoric acid as a by-product. Surprisingly, theaddition of phosphorus pentoxide as it is does not increase the amountof the phosphoric diester formed and can prevent the formation oforthophosphoric acid as a by-product. Further, the addition thereof canenhance the conversion by virtue of the high phosphorylating power ofphosphorus pentoxide.

After the addition of phosphorus pentoxide, the resulting mixture issubjected to the reaction under stirring at a temperature of generally40 to 120° C., preferably 60 to 100° C. for generally 1 to 24 hours,preferably 2 to 12 hours. When the reaction is conducted under suchconditions, the reaction will effectively advance, and, therefore, theconversion of the organic hydroxyl compound will be sufficiently highand the decomposition of phosphoric esters formed will not be liable toproceed.

Among various embodiments according to the present invention, anembodiment is preferable, which comprises conducting the reaction of thefirst step under such a condition that the ratio as defined by the aboveformula (II) exceeds 3.2 but is up to 6.4, preferably be 3.5 to 5, andthereafter adding phosphorus pentoxide in such an amount that the ratioas defined by the above formula (II) ranges from 2.8 to 3.2, preferably2.9 to 3.1 to the reaction system to conduct further phosphorylating.According to this embodiment, the phosphorylating can be generallyachieved substantially only by the above two steps. When thephosphorylating is conducted according to this embodiment, the viscosityincrease of the reaction system can be prevented during the reaction todispense with an equipment such as an intensive mixer.

Although the reaction product (phosphoric ester mixture) prepared by theabove process can be used as such, it is preferable for some uses thatthe reaction product be subjected to the following post-treatment.Specifically, when a phosphoric ester mixture containing a compoundhaving a pyrophosphate bond such as one represented by the followingformula (J) is used in the preparation of toiletries, the resultingtoiletries exhibit poor properties: ##STR4## wherein X represents ahydrogen atom or a residue obtained by eliminating one hydroxyl groupfrom an organic hydroxyl compound. Therefore, it is preferable that thephosphoric ester mixture be subjected to hydrolysis to cleave thepyrophosphate bond.

The hydrolysis is preferably conducted by adding 1 to 10% by weight(based on the obtained reaction product) of water to the reactionproduct (phosphoric ester mixture) and keeping the resulting mixture at60 to 100° C.

The phosphoric ester mixtures each comprising a phosphoric monoesterprepared according to the process of the present invention haverelatively good odor. In order to result in a further improvement of theodor, especially in cases of phosphoric monoester each having along-chain alkyl group, it is preferable that the phosphoric estermixture be subjected to deodorization. Although the deodorization may beconducted by any of steam distillation, extraction, crystallization andso forth, steam distillation is preferable with that using a thin filmbeing still more preferable.

The phosphoric monoester prepared by the process of the presentinvention and salts thereof can be used in a wide field as a detergent,a textile treatment agent, an emulsifying agent, a rust preventive, aliquid ion exchanger, a medicament or the like. The salts of themonoester includes salts thereof with alkali metals, alkaline earthmetals, alkanolamines, basic amino acids and so forth.

For example, in the preparation of a detergent composition containing aphosphoric monoester according to the present invention or a saltthereof, it is preferable that the monoester or salt be used in anamount of 2 to 60% by weight, particularly 10 to 40% by weight based onthe whole weight of the composition. In the preparation of the detergentcomposition, various surfactant which are commonly used in thepreparation of detergent compositions may be optionally used in additionto the above phosphoric monoester or the salt.

Examples of the anionic surfactant usable in this case include sulfate,sulfonate and carboxylate type surfactants. Specific examples of thesulfate and sulfonate type surfactants include salts of alkyl sulfates,salts of polyoxyethylene alkyl sulfates; and sulfosuccinate, taurate,isethionate and α-olefin sulfonate type surfactants, while those of thecarboxylate type surfactant include fatty acid soaps, ether carboxylatetype surfactants and acylated amino acid type surfactants.

Examples of the amphoteric surfactant usable in the above case includecarbobetaine type, phosphobetaine type, sulphobetaine type andimidazolinium betaine type surfactants.

Examples of the nonionic surfactant usable therein includepolyoxyalkylene addition type, polyoxypropylene-polyoxyethylene additiontype, amine oxide type and mono- and di-ethanolamide type surfactants;sorbitan fatty acid esters and adducts thereof with ethylene oxide;glycerol fatty acid esters and adducts thereof with ethylene oxide;sucrose esters and adducts thereof with ethylene oxide; alkylsaccharidetype surfactants and adducts thereof with ethylene oxide; andN-polyhydroxy-alkylfatty acid amide type surfactants.

Examples of the cationic surfactant usable therein include quaternaryammonium salts of linear or branched mono- or di-alkyl addition type andadducts thereof wherein alkylene oxide molecules are added to the alkylgroup.

These surfactants are each used alone or as a mixture of two or more ofthem. The amount of the surfactant is preferably 0.1 to 60% by weight,particularly preferably 1 to 50% by weight based on the whole weight ofthe detergent composition, though the amount varies depending upon theform of the composition.

The detergent composition containing a phosphoric monoester according tothe present invention may further contain one or more conventionalcomponents for detergent compositions in addition to the abovesurfactant components so far as the effects of the phosphoric monoesteraccording to the present invention are not impaired. The conventionalcomponents include polyhydric alcohols, e.g., ethylene glycol,diethylene glycol, triethylene glycol, polyethylene glycols wherein thedegree of polymerization is 4 or above, propylene glycol, dipropyleneglycol, polypropylene glycols wherein the degree of polymerization is 3or above, butylene glycols (such as 1,3-butylene glycol and 1,4-butyleneglycol), glycerol, diglycerol, polyglycerols wherein the degree ofpolymerization is 3 or above, sugar alcohols (such as sorbitol,mannitol, xylitol and maltitol), adducts of glycerols with ethyleneoxide (hereinafter abbreviated to "EO") and/or propylene oxide(hereinafter abbreviated at "PO"), adducts of sugar alcohols with EOand/or PO, saccharide (such as galactose, glucose, fructose, sucrose,maltose and lactose) and adducts thereof with EO and/or PO, andglycosides (such as methyl glycoside and ethyl glycoside) and adductsthereof with EO and/or PO; oil components, e.g., hydrocarbons (such asliquid paraffin, squalane, vaseline and solid paraffin), natural fatsand oils (such as olive oil, jojoba oil, evening primrose oil, coconutoil and beef tallow), ester oils (such as isopropyl myristate, cetylisooctanoate and neopentyl glycol dicaprate), silicone oils (such asmethyl silicone and methyl phenyl silicone), and higher fatty acids(such as isostearic acid and oleic acid); drugs, e.g., vitamines,antimicrobials (such as triclosan and trichlorocarban),anti-inflammatories (such as dipotassium glycyrrhetinate and tocopherolacetate), anti-dandruff agents (such as zinc pyrithione and Octopirox),activators, refrigerants (such as menthol), and ultraviolet absorbers;water swelling clayey minerals, e.g., montmorillonite, saponite,hectorite, veegum, kunipia, smecton; polymers, e.g., polysaccharides(such as carrageenan, xanthan gum, sodium alginate, pullulan, methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose andhydroxypropyl cellulose) and synthetic polymers (such as carboxyvinylpolymer and polyvinyl pyrrolidone); pigments, e.g., inorganic pigments(such as titanium oxide, kaolin, mica, sericite, zinc white and talc)and powdery polymers (such as polymethyl methacrylate and nylon powder);antiseptics, e.g., methyl paraben and butyl paraben; viscositymodifiers, e.g, inorganic salts, polyethylene glycol stearate andethanol; pearl ingredients; perfumes; dyestuffs; and antioxidants.

The detergent composition can be prepared by a conventional process.Although the detergent composition may take any form selected from amongliquid, paste, solid, powder and so forth, it is desirable that thecomposition takes a liquid or pasty form.

According to the process for the preparation of a phosphoric monoesterin the present invention, a phosphoric ester mixture which has anenhanced purity for a monoester and is reduced in the orthophosphoricacid (by-product) content can be prepared extremely easily. Further, thepresent invention enables the industrial preparation of a phosphoricmonoester excellent in odor and hue.

Although the reason why an excellent phosphoric monoester as describedabove can be prepared by the process of the present invention has notbeen elucidated as yet, it is presumed to be as follows: the directreaction of an organic hydroxyl compound with highly active phosphoruspentoxide gives diester and triester; in the present invention, however,phosphorus pentoxide is preliminary reacted with water, so that theactivity of phosphorus pentoxide is controlled to thereby give monoesterpreferentially. Further, with respect to the qualities, the directcontact of an organic hydroxyl compound or phosphoric esters with highlyactive phosphorus pentoxide is prevented in the present invention totherefore give a reaction product excellent in odor and hue.

The liquid detergent composition containing a phosphoric monoesterprepared by the process of the present invention does not harm the skinor hair and is excellent in ability to foam and stability, so that itcan be used as a detergent component for a product which comes intodirect contact with the skin for a long time, for example, kitchendetergent, as well as a shampoo and a body shampoo.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph showing the relationships between purity for aphosphoric monoester and orthophosphoric acid (as a by-product) ratewith respect to the reaction products which are prepared in Examples 1to 3 and Comparative Examples 1 to 3, respectively.

EXAMPLES

The present invention will now be described in more detail by referringto the following Examples and Comparative Examples, though the presentinvention is not limited to these Examples only.

In the Examples and Comparative Examples, all percentages are by weight,unless otherwise noted.

Example 1

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 37.2 g(0.258 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 0.5 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 0.67).

Then, 186.3 g (1.00 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. 24.0 g (0.167 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at90° C. for 6 hours to further conduct a reaction. During the aboveoperation, the reaction system was kept at low viscosity, so that noparticularly intensive mixer was necessitated.

Then, 13.4 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 2 hours to conducthydrolysis. The reaction product thus prepared comprised 76.8% ofmonolauryl phosphate, 13.0% of dilauryl phosphate, 5.9% oforthophosphoric acid and 4.3% of unreacted alcohol, exclusive of water.The hue of the product was 2 by klett.

Further, the reaction product was subjected to deodorization using asteam distillator (heat transfer area: 0.03 m², made of glass) withforced thin film. The steam distillation was conducted at a jackettemperature of 150° C. and 20 mmHg by continuously feeding the reactionproduct and steam at rates of 100 g/hr and 150 g/hr respectively to givean objective phosphoric monoester-containing product as a residue. Thedistillate was a mixture comprising unreacted alcohol and water. Theresidue comprised 80.0% of monolauryl phosphate, 13.6% of dilaurylphosphate, 6.2% of orthophosphoric acid and 0.24% of unreacted alcohol,exclusive of water. The hue klett of the residue was 3 and the odorthereof was good as evaluated organoleptically.

The analysis of the reaction product (or the residue) was conducted asfollows: (Analyses for a phosphoric monoester, a phosphoric diester andorthophosphoric acid)

The reaction product was subjected to extraction with diethyl ether toconduct the partition of the product between the ether and water, givingan aqueous phase containing orthophosphoric acid and an organic phasecontaining a phosphoric monoester and a phosphoric diester. Each phasewas subjected to potentiometric titration to determine theorthophosphoric acid content.

More specifically, about 5 g (a g) of a sample, 100 ml of 0.1Nhydrochloric acid and 100 ml of diethyl ether were put in a 500-mlseparatory funnel. The resulting funnel was vigorously shaken andthereafter allowed to stand, by which the contents were separated intotwo phases. The lower layer (aqueous phase) was subjected topotentiometric titration with an 0.5N aqueous solution of potassiumhydroxide to determine the amount (b mol) of alkali consumed until thereaction reached the first equivalence point and that (c mol) thereofconsumed until the reaction reached the second equivalence point. Theorthophosphoric acid content was calculated according to the followingformula (1): ##EQU6##

The organic phase was distilled to remove the ether. Tetrahydrofuran wasadded to the residue to make up to a total amount of 100 ml. 10 ml ofthe resulting mixture was sampled with a transfer pipette and added to amixture comprising 55 ml of tetrahydrofuran and 35 ml of deionizedwater, followed by dissolution. The obtained solution was subjected topotentiometric titration with a 0.5N aqueous solution of potassiumhydroxide to determine the amount (d mol) of alkali consumed until thereaction reached the first equivalence point and that (e mol) thereofconsumed until the reaction reached the second equivalence point. Thephosphoric monoester content and the phosphoric diester content weredetermined according to the following formulae (2) and (3): ##EQU7##(Analysis for Unreacted Organic Hydroxyl Compound)

The analysis for unreacted organic hydroxyl compound was conducted byextraction with petroleum ether. More specifically, 5 to 10 g of asample was dissolved in a mixture comprising 100 ml of isopropanol and100 ml of 15% by weight aqueous solution of triethanolamine. Theobtained solution was transferred to a 500-ml separatory funnel andextracted with 100 ml of petroleum ether thrice. The petroleum etherphases were combined each other and washed with 100 ml of 50% by volumeaqueous solution of ethanol twice and with 100 ml of deionized wateronce. The resulting petroleum ether phase was dried over anhydroussodium sulfate and then distilled to remove the petroleum ether. Theresulting residue (petroleum ether extract) was dried at roomtemperature under a reduced pressure (about 200 mmHg) until a constantweight was reached. The weight of the petroleum ether extract wasaccurately determined.

Further, the hue was determined by the following method.

The reaction product was diluted with a solvent such as ethanol andtetrahydrofuran to 10 w/v % , or the residue was dissolved in such asolvent in a concentration of 10 w/v %. The absorbance of the obtainedsolution was determined at 420 nm and multiplied by 1000. The obtainedvalue was given as klett. A higher klett means severer yellowing, whilea lower klett means nearer colorless. It is preferable that the klett be15 or below, still more preferably 10 or below.

The odor was evaluated organoleptically. Comparative Example 1

186.3 g (1.00 mol) of lauryl alcohol (MW: 186.3) and 75% phosphoricacid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g (0.5 mol)], werefed into a reactor (capacity: 1000 ml). The obtained mixture was stirredat 50° C. for 0.5 hour.

Then, phosphorus pentoxide (active ingredient: 98.5%), 61.2 g (0.425mol), was gradually added to the obtained mixture at 50° C. and afterthe completion of the addition, the resulting mixture was kept at 90° C.for 10 hours to conduct a reaction.

Then, 13.4 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° for 2 hours to conduct hydrolysis.The reaction product thus prepared comprised 72.3% of monolaurylphosphate, 16.6% of dilauryl phosphate, 6.8% of orthophosphoric acid and4.3% of unreacted alcohol, exclusive of water. The hue klett of theproduct was 20.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 75.3% of monolauryl phosphate, 17.3% of dilaurylphosphate, 7.1% of orthophosphoric acid and 0.31% of unreacted alcohol,exclusive of water. The hue klett of the residue was 30 and the odorthereof was nasty as evaluated organoleptically.

Example 2

75% phosphoric acid, 15.8 g [(P₂ O₅ : 8.59 g (0.061 mol), water: 7.21 g(0.401 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 39.2g (0.272 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 0.5 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 0.83).

Then, 204.9 g (1.10 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. 24.0 g (0.167 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3.02) was keptat 90° C. for 6 hours to further ccnduct a reaction. During the aboveoperation, the reaction system was kept at low viscosity, so that noparticularly intensive mixer was necessitated.

Then, 14.2 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 2 hours to conducthydrolysis. The reaction product thus prepared comprised 76.7% ofmonolauryl phosphate, 16.1% of dilauryl phosphate, 3.6% oforthophosphoric acid and 3.6% of unreacted alcohol, exclusive of water.The hue klett of the product was 2.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 79.4% of monolauryl phosphate, 16.7% of dilaurylphosphate, 3.7% of orthophosphoric acid and 0.26% of unreacted alcohol,exclusive of water. The hue klett of the residue was 3 and the odorthereof was good as evaluated organoleptically.

Comparative Example 2

204.9 g (1.10 mol) of lauryl alcohol (MW: 186.3) and 75% phosphoricacid, 15.8 g [P₂ O₅ : 8.58 g (0.060 mol), water: 7.22 g (0.401 mol)],were fed into a reactor (capacity: 1000 ml). The obtained mixture wasstirred at 50° C. for 0.5 hour.

Then, phosphorus pentoxide (active ingredient: 98.5%), 63.4 g (0.44mol), was gradually added to the obtained mixture at 50° C. and afterthe completion of the addition, the resulting mixture was kept at 80° C.for 12 hours to conduct a reaction.

Then, 14.2 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 80° C. for 3 hours to conducthydrolysis. The reaction product thus prepared comprised 72.1% ofmonolauryl phosphate, 19.9% of dilauryl phosphate, 3.8% oforthophosphoric acid and 4.2% of unreacted alcohol, exclusive of water.The hue klett of the product was 18.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 75.0% of monolauryl phosphate, 20.7% of dilaurylphosphate, 4.0% of orthophosphoric acid and 0.29% of unreacted alcohol,exclusive of water. The hue klett of the residue was 25 and the odorthereof was nasty as evaluated organoleptically.

Example 3

85% phosphoric acid, 28.2 g [P₂ O₅ : 17.4 g (0.123 mol), water: 10.8 g(0.600 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 30.3g (0.210 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 0.5 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 0.56).

Then, 167.7 g (0.90 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. 24.0 g (0.167 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at90° C. for 6 hours to further conduct a reaction. During the aboveoperation, the reaction system was kept at low viscosity, so that noparticularly intensive mixer was necessitated.

Then, 12.5 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 2 hours to conducthydrolysis. The reaction product thus prepared comprised 79.7% ofmonolauryl phosphate, 7.2% of dilauryl phosphate, 8.4% oforthophosphoric acid and 4.7% of unreacted alcohol, exclusive of water.The hue klett of the product was 2.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 83.4% of monolauryl phosphate, 7.5% of dilaurylphosphate, 8.8% of orthophosphoric acid and 0.22% of unreacted alcohol,exclusive of water. The hue klett of the residue was 3 and the odorthereof was good as evaluated organoleptically.

Comparative Example 3

167.7 g (0.9 mol) of lauryl alcohol (MW: 186.3) and 85% phosphoric acid,28.2 g [P₂ O₅ : 17.4 g (0.123 mol), water: 10.8 g (0.6 mol)], were fedinto a reactor (capacity: 1000 ml). The obtained mixture was stirred at50° C. for 0.5 hour.

Then, phosphorus pentoxide (active ingredient: 98.5%), 54.3 g (0.377mol), was gradually added to the obtained fixture at 50° C. and afterthe completion of the addition, the resulting mixture was kept at 90° C.for 10 hours to conduct a reaction.

Then, 12.5 of deionized water was added to the reaction mixture and theresulting mixture was kept at 90° C. for 2 hours to conduct hydrolysis.The reaction product thus prepared comprised 75.4% of monolaurylphosphate, 11.7% of dilauryl phosphate, 8.4% of orthophosphoric acid and4.5% of unreacted alcohol, exclusive of water. The hue klett of theproduct was 30.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 78.7% of monolauryl phosphate, 12.2% of dilaurylphosphate, 8.8% of orthophosphoric acid and 0.33% of unreacted alcohol,exclusive of water. The hue klett of the residue was 38 and the odorthereof was nasty as evaluated organoleptically.

Example 4

105% polyphosphoric acid, 37.6 g [(P₂ O₅ : 28.6 g (0.202 mol), water:9.0 g (0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%),18.9 g (0.131 mol), were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 70° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.67).

Then, 186.3 g (1.00 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 70° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 70° C. for onehour to conduct a reaction. 24.0 g (0.167 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 70° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at90° C. for 6 hours to further conduct a reaction. During the aboveoperation, the reaction system was kept at low viscosity, so that noparticularly intensive mixer was necessitated.

Then, 26.7 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 80° C. for 3 hours to conducthydrolysis. The reaction product thus prepared comprised 76.0% ofmonolauryl phosphate, 13.5% of dilauryl phosphate, 6.1% oforthophosphoric acid and 4.4% of unreacted alcohol, exclusive of water.The hue klett of the product was 3.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 79.3% of monolauryl phosphate, 14.1% of dilaurylphosphate, 6.4% of orthophosphoric acid and 0.25% of unreacted alcohol,exclusive of water. The hue klett of the residue was 4 and the odorthereof was good as evaluated organoleptically.

Example 5

85% phosphoric acid, 23.5 g [P₂ O₅ : 14.5 g (0.102 mol), water: 9.0 g(0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 33.3 g(0.234 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 0.5 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 0.67).

Then, 172.9 g (1.00 mol) of undecanol (Neodol 1, a product of Shell, MW:172.9) was added to the heterogeneous phosphorylating agent at 50° C.and the obtained mixture (the ratio as defined by formula (II): 4.46)was kept at 50° C. for 3 hours to conduct a reaction. 24.0 g (0.167 mol)of phosphorus pentoxide (active ingredient: 98.5%) was gradually addedto the obtained reaction mixture at 50° C. in 2 hours. After thecompletion of the addition, the resulting mixture (the ratio as definedby formula (II): 2.98) was kept at 90° C. for 8 hours to further conducta reaction. During the above operation, the reaction system was kept atlow viscosity, so that no particularly intensive mixer was necessitated.

Then, 12.7 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 3 hours to conducthydrolysis. The reaction product thus prepared comprised 75.9% ofmonoundecyl phosphate, 13.6% of diundecyl phosphate, 6.6% oforthophosphoric acid and 3.9% of unreacted alcohol, exclusive of water.The hue klett of the product was 3.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 78.8% of monoundecyl phosphate, 14.1% of diundecylphosphate, 6.9% of orthophosphoric acid and 0.20% of unreacted alcohol,exclusive of water. The hue klett of the residue was 4 and the odorthereof was good as evaluated organoleptically.

Example 6

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 37.2 g(0.258 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 60° C. for 0.5 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 0.67).

Then, 190.7 g (1.00 mol) of Diadol 115L (a product of MitsubishiChemical Co. Ltd., MW: 190.7) was added to the heterogeneousphosphorylating agent at 60° C. and the obtained mixture (the ratio asdefined by formula (II): 4.5) was kept at 60° C. for 2 hours to conducta reaction. 24.0 g (0.167 mol) of phosphorus pentoxide (activeingredient: 98.5%) was gradually added to the obtained reaction mixtureat 60° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at80° C. for 10 hours to further conduct a reaction. During the aboveoperation, the reaction system was kept at low viscosity, so that noparticularly intensive mixer was necessitated.

Then, 27.2 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 2 hours to conducthydrolysis. The reaction product thus prepared comprised 76.0% ofmonoalkyl phosphate, 13.8% of dialkyl phosphate, 6.1% of orthophosphoricacid and 4.1% of unreacted alcohol, exclusive of water. The hue klett ofthe product was 2.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 79.1% of monoalkyl phosphate, 14.4% of dialkylphosphate, 6.3% of orthophosphoric acid and 0.25% of unreacted alcohol,exclusive of water. The hue klett of the residue was 3 and the odorthereof was good as evaluated organoleptically.

Example 7

85% phosphoric acid, 23.5 g [P₂ O₅ : 14.5 g (0.102 mol), water: 9.0 g(0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 33.3 g(0.231 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 1.0 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 0.67).

Then, 272.5 g (1.00 mol) of stearyl alcohol (MW: 272.5) was added to theheterogeneous phosphorylating agent at 80° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for 2hours to conduct a reaction. 24.0 g (0.167 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at100° C. for 3 hours to further conduct a reaction. During the aboveoperation, the reaction system was kept at low viscosity, so that noparticularly intensive mixer was necessitated.

Then, 17.7 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 3 hours to conducthydrolysis. The reaction product thus prepared comprised 76.2% ofmonostearyl phosphate, 14.6% of distearyl phosphate, 4.7% oforthophosphoric acid and 4.5% of unreacted alcohol, exclusive of water.The hue klett of the product was 3 and the odor thereof was good asevaluated organoleptically.

Comparative Example 4

272.5 g (1.0 mol) of stearyl alcohol (MW: 272.5) and 85% phosphoricacid, 23.5 g [P₂ O₅ : 14.5 g (0.102 mol), water: 9.0 g (0.5 mol)], werefed into a reactor (capacity: 1000 ml). The obtained mixture was stirredat 80° C. for 0.5 hour.

Then, phosphorus pentoxide (active ingredient: 98.5%), 57.3 g (0.398mol), was gradually added to the obtained mixture at 80° C. and afterthe completion of the addition, the resulting mixture was kept at 90° C.for 8 hours to conduct a reaction.

Then, 17.7 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 2 hours to conducthydrolysis. The reaction product thus obtained comprised 70.8% ofmonostearyl phosphate, 19.0% of distearyl phosphate, 5.0% oforthophosphoric acid and 5.2% of unreacted alcohol, exclusive of water.The hue klett of the product was 30 and the odor thereof was nasty asevaluated organoleptically.

Example 8

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%). 61.2 g(0.425 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 0.5 hour to prepare a heterogeneousphosphorylating agent (the ratio as defined by formula (I): 1).

Then, 186.3 g (1.00 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 3) was kept at 90° C. for 8 hoursto conduct a reaction. In the course of the reaction, the reactionsystem became viscous, so that the system was stirred with an intensivemixer.

Then, 13.4 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 2 hours to conducthydrolysis. The reaction product thus prepared comprised 77.0% ofmonolauryl phosphate, 14.1% of dilauryl phosphate, 5.2% oforthophosphoric acid and 3.7% of unreacted alcohol, exclusive of water.The hue klett of the product was 3.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 79.8% of monolauryl phosphate, 14.6% of dilaurylphosphate, 5.4% of orthophosphoric acid and 0.22% of unreacted alcohol,exclusive of water. The hue klett of the residue was 4 and the odorthereof was good as evaluated organoleptically.

Example 9

85% phosphoric acid, 23.5 g [P₂ O₅ : 14.5 g (0.102 mol), water: 9.0 g(0.5 mol)], and phosphorus pentoxide (active ingredient: 98.5%), 57.3 g(0.401 mol), were fed into a reactor (capacity: 1000 ml). The obtainedmixture was stirred at 50° C. for 0.5 hour.

Then, 172.9 g (1.00 mol) of undecanol (Neodol 1, a product of Shell, MW:172.9) was added to the heterogeneous phosphorylating agent at 50° C.and the obtained mixture (the ratio as defined by formula (II): 2.98)was kept at 90° C. for 8 hours to conduct a reaction. In the course ofthe reaction, the reaction system became viscous, so that the system wasstirred with an intensive mixer.

Then, 12.7 g of deionized water was added to the reaction mixture andthe resulting mixture was kept at 90° C. for 3 hours to conducthydrolysis. The reaction product thus prepared comprised 76.2% ofmonoundecyl phosphate, 14.0% of diundecyl phosphate, 5.8% oforthophosphoric acid and 4.0% of unreacted alcohol, exclusive of water.The hue klett of the product was 3.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 79.2% of monoundecyl phosphate, 14.6% of diundecylphosphate, 6.0% of orthophosphoric acid and 0.20% of unreacted alcohol,exclusive of water. The hue klett of the residue was 4 and the odor ofthe residue was good as evaluated organoleptically.

The results of Examples 1 to 9 and Comparative Examples 1 to 4 are givenin Table 1, wherein the purity for a phosphoric monoester,orthophosphoric acid (as a by-product) rate, hue and odor of thereaction product and the conversion of the starting organic hydroxylcompound are described. Further, FIG. 1 shows the relationships betweenpurity for a phosphoric monoester and orthophosphoric acid (as aby-product) rate with respect to the reaction products which areprepared in Examples 1 to 3 and Comparative Examples 1 to 3,respectively.

As apparent from the results of Table 1 and FIG. 1, the phosphorylatingof an organic hydroxyl compound with phosphorus pentoxide in thepresence of water is characterized in that as the ratio of water to anorganic hydroxyl compound increases, the purity for a phosphoricmonoester of the product increases with increase in the orthophosphoricacid rate of the product. When an Example product is compared with aComparative product, the purity of the Example product for a phosphoricmonoester is higher than that of Comparative product for a phosphoricmonoester, when the orthophosphoric acid rates of both products are thesame, while the orthophosphoric acid rate of the Example product islower than that of the Comparative product, when the purities of bothproducts for phosphoric monoester are the same. Further, the products ofExamples 1 to 9 are also excellent in hue. Furthermore, the aboveresults revealed that the products of Examples 1 to 9, including bothdeodorized and undeodorized ones, are superior to those of ComparativeExamples in odor.

Accordingly, it can be understood that the process of the presentinpreparationbles the preparation of a phosphoric ester mixture whichhas an enhanced purity for a phosphoric monoester, is reduced in theorthophosphoric acid (as a by-product) rate and exhibits good odor andhue.

                                      TABLE 1                                     __________________________________________________________________________               Ratio of total feeds                                                 Kind of of starting materials Purity for a                                    organic organic hydroxyl phosphoric Orthophosphoric                           hydroxyl compound/water/P.sub.2 O.sub.5 monoester*.sup.1 acid rate*.sup.                                                  2 Hue*.sup.3 Odor after                                                        compound (molar ratio) (wt                                                   %) (wt %) klett deodorizatio                                                  n Conversion*.sup.5             __________________________________________________________________________    Ex. 1                                                                             lauryl alcohol                                                                       2.0/1.0/1 85.5  6.57    2   good   93.8                              Comp. lauryl alcohol 2.0/1.0/1 81.3 7.65 20 nasty 93.8                        Ex. 1                                                                         Ex. 2 lauryl alcohol 2.2/0.8/1 82.7 3.88 2 good 95.0                          Comp. lauryl alcohol 2.2/0.8/1 78.4 4.13 18 nasty 94.0                        Ex. 2                                                                         Ex. 3 lauryl alcohol 1.8/1.2/1 91.7 9.67 2 good 93.0                          Comp. lauryl alcohol 1.8/1.2/1 86.6 9.64 30 nasty 93.3                        Ex. 3                                                                         Ex. 7 stearyl 2.0/1.0/1 83.9 5.18 3 good*.sup.4 94.0                           alcohol                                                                      Comp. stearyl 2.0/1.0/1 78.8 5.57 30 nasty*.sup.4 93.3                        Ex. 4 alcohol                                                                 Ex. 4 lauryl alcohol 2.0/1.0/1 84.9 6.82 3 good 93.5                          Ex. 5 Neodol 1 2.0/1.0/1 84.8 7.37 3 good 94.1                                Ex. 6 Diadol 115L 2.0/1.0/1 84.6 6.79 2 good 94.2                             Ex. 8 lauryl alcohol 2.0/1.0/1 84.5 5.71 3 good 94.6                          Ex. 9 Neodol 1 2.0/1.0/1 84.5 6.43 3 good 94.1                              __________________________________________________________________________

notes)

1: the purity of the reaction product (before deodorization) for aphosphoric monoester as calculated according to the following formula##EQU8## 2: the orthophosphoric acid rate of the reaction product(before deodorization) as calculated according to the following formula##EQU9## 3: the hue of the reaction product (before deodorization) 4:the odor of the reaction product (before deodorization)

5: the conversion of an organic hydroxyl compound as calculatedaccording to the following formula: ##EQU10##

Comparative Examples will now be described to explain why the mixingratio of starting materials is limited in the present invention.

Comparative Example 5

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and 18.0 g (0.125 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.4).

Then, 186.3 g (1.00 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 7.5) was kept at 80° C. for onehour to conduct a reaction. Phosphorus pentoxide (active ingredient:98.5%), 43.2 g (0.3 mol), was gradually added to the obtained reactionmixture at 80° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at90° C. for 6 hours to further conduct a reaction.

Then, 13.4 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 72.0%of monolauryl phosphate, 16.2% of dilauryl phosphate, 6.6% oforthophosphoric acid and 5.2% of unreacted alcohol, exclusive of water.The hue klett of the product was 13.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 75.6% of monolauryl phosphate, 17.0% of dilaurylphosphate, 6.9% of orthophosphoric acid and 0.5% of unreacted alcohol,exclusive of water. The hue klett of the residue was 15 and the odorthereof was nasty as evaluated organoleptically.

Comparative Example 6

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and 18.0 g (0.125 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.4).

Then, 74.5 g (0.4 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. Phosphorus pentoxide (active ingredient:98.5%), 14.4 g (0.1 mol), was gradually added to the obtained reactionmixture at 80° C. in 2 hours. After the completion of the addition, theresulting mixture (the ratio as defined by formula (II): 3) was kept at90° C. for 6 hours to further conduct a reaction.

Then, 6.3 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 67.3%of monolauryl phosphate, 6.1% of dilauryl phosphate, 20.3% oforthophosphoric acid and 6.3% of unreacted alcohol, exclusive of water.The hue klett of the product was 12.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 71.5% of monolauryl phosphate, 6.5% of dilaurylphosphate, 21.6% of orthophosphoric acid and 0.4% of unreacted alcohol,exclusive of water. The hue klett of the residue was 14 and the odorthereof was nasty as evaluated organoleptically.

Comparative Example 7

In order to prepare a phosphorylating agent wherein the ratio as definedby formula (I) is 1.2, 75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g(0.075 mol), water: 9.0 g (0.5 mol)], and 75.7 g (0.525 mol) ofphosphorus pentoxide (active ingredient: 98.5%) were fed into a reactor(capacity: 1000 ml) and the obtained mixture was stirred. The systemturned into glassy solid, which could not be stirred.

Comparative Example 8

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water; 9.0 g(0.5 mol)], and 37.2 g (0.258 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.67).

Then, 62.0 g (0.333 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 2.5) was kept at 80° C. for onehour to conduct a reaction. 30.9 g (0.166 mol) of lauryl alcohol (MW:186.3) was added to the obtained reaction mixture and after thecompletion of the addition, the resulting mixture (the ratio as definedby formula (II): 3) was kept at 90° C. for 6 hours to further conduct areaction.

Then, 7.5 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 68.4%of monolauryl phosphate, 7.6% of dilauryl phosphate, 16.8% oforthophosphoric acid and 7.2% of unreacted alcohol, exclusive of water.The hue klett of the product was 14.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 73.2% of monolauryl phosphate, 8.2% of dilaurylphosphate, 18.0% of orthophosphoric acid and 0.6% of unreacted alcohol,exclusive of water. The hue klett of the residue was 18 and the odorthereof was nasty as evaluated organoleptically.

Comparative Example 9

75% phosphoric acid, 19.7 g [(P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and 37.2 g (0.258 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.67).

Then, 341.1 g (1.83 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 7.0) was kept at 80° C. for onehour to conduct a reaction. 64.0 g (0.444 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours and after the completion of the addition,the resulting mixture (the ratio as defined by formula (II): 3) was keptat 90° C. for 6 hours to further conduct a reaction.

Then, 23.1 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 62.1%of monolauryl phosphate, 29.2% of dilauryl phosphate, 3.3% oforthophosphoric acid and 5.4% of unreacted alcohol, exclusive of water.The hue klett of the product was 18.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 65.0% of monolauryl phosphate, 30.5% of dilaurylphosphate, 3.5% of orthophosphoric acid and 1.0% of unreacted alcohol,exclusive of water. The hue klett of the residue was 20 and the odorthereof was nasty as evaluated organoleptically.

Comparative Example 10

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and 37.2 g (0.258 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.67).

Then, 186.3 g (1.0 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. 17.6 g (0.122 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours and after the completion of the addition,the resulting mixture (the ratio as defined by formula (II): 3.3) waskept at 90° C. for 6 hours to further conduct a reaction.

Then, 13.0 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 66.3%of monolauryl phosphate, 16.8% of dilauryl phosphate, 6.1% oforthophosphoric acid and 10.8% of unreacted alcohol, exclusive of water.The hue klett of the product was 15.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 73.7% of monolauryl phosphate, 18.7% of dilaurylphosphate, 6.8% of orthophosphoric acid and 0.8% of unreacted alcohol,exclusive of water. The hue klett of the residue was 19 and the odorthereof was nasty as evaluated organoleptically.

Comparative Example 11

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and 37.2 g (0.258 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.67).

Then, 186.3 g (1.0 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. 38.5 g (0.267 mol) of phosphorus pentoxide(active ingredient: 98.5%) was gradually added to the obtained reactionmixture at 80° C. in 2 hours and after the completion of the addition,the resulting mixture (the ratio as defined by formula (II): 2.5) waskept at 90° C. for 6 hours to further conduct a reaction.

Then, 14.1 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 65.9%of monolauryl phosphate, 16.6% of dilauryl phosphate, 12.9% oforthophosphoric acid and 4.6% of unreacted alcohol, exclusive of water.The hue klett of the product was 15.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 68.7% of monolauryl phosphate, 17.3% of dilaurylphosphate, 13.5% of orthophosphoric acid and 0.5% of unreacted alcohol,exclusive of water. The hue klett of the residue was 18 and the odorthereof was nasty as evaluated organoleptically.

Comparative Example 12

75% phosphoric acid, 19.7 g [P₂ O₅ : 10.7 g (0.075 mol), water: 9.0 g(0.5 mol)], and 37.2 g (0.258 mol) of phosphorus pentoxide (activeingredient: 98.5%) were fed into a reactor (capacity: 1000 ml). Theobtained mixture was stirred at 50° C. for 0.5 hour to prepare aheterogeneous phosphorylating agent (the ratio as defined by formula(I): 0.67).

Then, 186.3 g (1.0 mol) of lauryl alcohol (MW: 186.3) was added to theheterogeneous phosphorylating agent at 50° C. and the obtained mixture(the ratio as defined by formula (II): 4.5) was kept at 80° C. for onehour to conduct a reaction. 116% (calculated as P₂ O₅) polyphosphoricacid. 56.2 g [P₂ O₅ : 47.2 g (0.333 mol), water: 9.0 g (0.5 mol)], wasadded to the obtained reaction mixture at 80° C. and the resultingmixture (the ratio as defined by formula (II): 3) was kept at 90° C. for6 hours to further conduct a reaction.

Then, 15.0 g of deionized water was added to the obtained reactionmixture and the resulting mixture was kept at 90° C. for 2 hours toconduct hydrolysis. The reaction product thus prepared comprised 67.5%of monolauryl phosphate, 6.7% of dilauryl phosphate, 17.3% oforthophosphoric acid and 8.5% of unreacted alcohol, exclusive of water.The hue klett of the product was 7.

Further, the reaction product was subjected to deodorization using asteam distillator with forced thin film. The steam distillation wasconducted under the same conditions as those of Example 1. The obtainedresidue comprised 73.4% of monolauryl phosphate, 7.3% of dilaurylphosphate, 18.8% of orthophosphoric acid and 0.5% of unreacted alcohol,exclusive of water. The hue klett of the residue was 10 and the odorthereof was nasty as evaluated organoleptically.

The results of Comparative Examples 5 to 12 are given in Table 2,wherein the purity for a phosphoric monoester, orthophosphoric acid (asa by-product) rate, hue and odor of the product and the conversion ofthe starting organic hydroxyl compound are described.

The notes *1 to *3 and *5 in Table 2 are the same as those in Table 1.

                                      TABLE 2                                     __________________________________________________________________________               Ratio of total feeds                                                  of starting materials Purity for a                                           Kind of org. organic hydroxyl phosphoric Orthophosphoric                      hydroxyl compound/water/P.sub.2 O.sub.5 monoester*.sup.1 acid rate*.sup.                                                  2 Hue*.sup.3 Odor after                                                       Conversion*.sup.5                 compound (molar ratio) (wt %) (wt %) klett deodorization (%)                __________________________________________________________________________    Comp.                                                                             lauryl alcohol                                                                       2.0/1.0/1 81.6  7.5     13  nasty  92.5                              Ex. 5                                                                         Comp. lauryl alcohol 2.0/2.5/1.5 91.7 27.7 14 nasty 89.2                      Ex. 6                                                                         Comp. lauryl alcohol 1.5/1.5/1.0 90.0 22.1 14 nasty 88.2                      Ex. 8                                                                         Comp. lauryl alcohol 3.7/1.0/1.6 68.0 3.6 18 nasty 92.7                       Ex. 9                                                                         Comp. lauryl alcohol 2.0/1.0/0.9 79.8 7.3 15 nasty 84.9                       Ex. 10                                                                        Comp. lauryl alcohol 2.0/1.0/1.2 79.9 15.6 15 nasty 92.8                      Ex. 11                                                                        Comp. lauryl alcohol 1.5/1.5/1.0 91.0 23.3  7 nasty 86.0                      Ex. 12                                                                      __________________________________________________________________________

There will now be described Formulation Examples with respect to thedetergent composition using the phosphoric monoester prepared in theabove Example. Formulation Example 1 (shampoo)

    ______________________________________                                        (1)   sodium lauryl ether sulfate                                                                          12%                                                (2) coconut oil fatty acid diethanolamide 3%                                  (3) Na salt of the phosphoric monoester 10%                                    prepared in Example 1                                                        (4) cationized cellulose 0.2%                                                 (5) fragrance 0.5%                                                            (6) water the balance                                                       ______________________________________                                    

According to the above formulation, the above components (1) to (4) wereadded to hot water (6) to conduct dissolution. The obtained solution wascooled, followed by the addition of the above component (5). Atransparent shampoo was prepared. When the hair was washed with thisshampoo, the shampoo was lowly irritant, exhibited a high ability tofoam a nd was excellent in feelings in use.

Formulation Example 2 (body shampoo)

    ______________________________________                                        (1)   Na salt of the phosphoric monoester                                                                  15%                                                 prepared in Example 1                                                        (2) lauroylamidopropyldimethylcarboxy- 3%                                      betaine                                                                      (3) lauryl dimethyl hydroxysulfobetaine 1%                                    (4) coconut oil fatty acid 4%                                                 (5) triethanolamine 4%                                                        (6) dibutylhydroxytoluene 0.1%                                                (7) ethanol 2%                                                                (8) fragrance 0.5%                                                            (9) water the balance                                                       ______________________________________                                    

According to the above formulation, the above components (1) to (6) wereadded to hot water (9) to conduct dissolution. The obtained solution wascooled, followed by the addition of the above components (7) and (8). Atransparent body shampoo was prepared. When the skin was washed withthis body shampoo, the shampoo was lowly irritant, exhibited a highability to foam and was excellent in feelings in use.

We claim:
 1. A process for the preparation of a phosphoric monoestercomprising:(1) a first step of reacting an organic hydroxyl compoundwith a pre-mixed phosphorylating agent consisting essentially ofphosphorus pentoxide and at least one compound selected from the groupconsisting of water, phosphoric acid and polyphosphoric acid, under suchconditions that a) the ratio as defined by formula (I) has a value inthe range of from 0.5 to 1.0 and b) the ratio as defined by formula (II)has a value in the range of from exceeding 3.2 up to 6.4, and (2) asecond step, wherein phosphorus pentoxide is added in such an amountthat the ratio represented by formula (II) has a value in the range offrom 2.8 to 3.2: ##EQU11##
 2. The process according to claim 1; whereinthe phosphorylating agent comprises phosphorus pentoxide and at leastone compound selected from the group consisting of water and phosphoricacid.
 3. The process according to claim 1, which further comprises astep of hydrolysis of the reaction product.
 4. The process according toclaim 1, which further comprises a step of deodorization.
 5. The processaccording to claim 1, wherein the organic hydroxyl compound is a linearor branched, saturated or unsaturated alcohol having 6 to 30 carbonatoms, an adduct of a linear or branched, saturated or unsaturatedalcohol having 6 to 30 carbon atoms with 1 or more alkylene oxide(s),wherein the alkylene oxide has 2 to 4 carbon atoms and the number ofalkylene oxide molecules added is 1 to 100, or an adduct of analkylphenol, wherein the alkyl moiety has 6 to 20 carbon atoms, with 1or more alkylene oxide(s), wherein the alkylene oxide has 2 to 4 carbonatoms and the number of alkylene oxide molecules added is 1 to 100.